Double hydrophilic block copolymer monolayer protected hybrid gold nanoparticles and their shell cross-linking

J Phys Chem B. 2005 Dec 1;109(47):22159-66. doi: 10.1021/jp0549935.

Abstract

This paper describes the syntheses of core/shell gold nanoparticles stabilized with a monolayer of double hydrophilic block copolymer and their stimuli responsiveness before and after shell cross-linking. The hybrid nanoparticles consist of gold core, cross-linkable poly(2-(dimethylamino)ethyl methacrylate) (PDMA) inner shell, and poly(ethylene oxide) (PEO) corona. First, diblock copolymer PEO-b-PDMA was prepared via the reversible addition-fragmentation chain transfer (RAFT) technique using a PEO-based macroRAFT agent. The dithioester end group of PEO-b-PDMA diblock copolymer was reduced to a thiol end group. The obtained PEO-b-PDMA-SH was then used to prepare diblock copolymer stabilized gold nanoparticles by the "grafting-to" approach. 1,2-Bis(2-iodoethoxy)ethane (BIEE) was utilized to selectively cross-link the PDMA residues in the inner shell. The stimuli responsiveness and colloidal stability of core/shell gold nanoparticles before and after shell cross-linking were characterized by laser light scattering (LLS), UV-vis transmittance, and transmission electron microscopy (TEM). At pH 9, the average hydrodynamic radius Rh of non-cross-linked hybrid gold nanoparticles starts to increase above 35 degrees C due to the lower critical solution temperature (LCST) phase behavior of the PDMA blocks in the inner shell. In contrast, Rh of the shell cross-linked gold nanoparticles were essentially independent of temperature. Core/shell gold nanoparticles before and after shell cross-linking exhibit reversible swelling on varying the solution pH. Compared to non-cross-linked core/shell gold nanoparticles, shell cross-linking of the hybrid gold nanoparticles leads to permanent core/shell nanostructures with much higher colloidal stability and physically isolates the gold core from the external environment.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Gold / chemistry*
  • Hydrogen-Ion Concentration
  • Hydrophobic and Hydrophilic Interactions
  • Membranes, Artificial*
  • Methacrylates / chemical synthesis
  • Methacrylates / chemistry*
  • Molecular Structure
  • Nanoparticles / chemistry*
  • Nylons / chemistry*
  • Particle Size
  • Polyethylene Glycols / chemical synthesis
  • Polyethylene Glycols / chemistry*
  • Surface Properties
  • Temperature

Substances

  • Membranes, Artificial
  • Methacrylates
  • Nylons
  • poly(2-(dimethylamino)ethyl methacrylate)
  • poly(ethylene oxide)-block-poly(2-((dimethylamino)ethyl methacrylate))
  • Polyethylene Glycols
  • Gold